Detergent composition



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DETERGENT COMPOSITION Vladimir Dvorkovitz, Kansas City, Mo., and Neil W.Berst and George G. Leist, Evanston, 111., assignors to The DiverseyCorporation, a corporation of Illinois No Drawing. Filed July 15, 1955,Ser. No. 522,371

2 Claims, (Cl. 252-152) This invention relates to additives that reducethe skin irritation that is normally associated with the use ofdetergent formulations, the commercial application of said additives anddetergent formulations containing said additives.

We "have discovered that when water-soluble acids such as a N-higheracyl sarcosin and/or water-soluble salts of said acids such as sodiumN-lauroy-l sarcosimate, as well as materials that form said salts and/oracids upon hydration or when in contact with the skin, are combined withdetergents or detergent solutions (i.e., aqueous solutions, etc.), theytend to reduce the skin irritation that is normally associated withdetergent formulations. The water-soluble salts include alkali metal,amine and ammonium salts; the salts have been found to be generally aseiiective as the corresponding free acid. These materials shall hereinbe referred to as additive(s) The additives, as well as combinations ofthe additives, are particularly eiiective when used in conjunction withalkaline detergents; however, they may also be employed withsubstantially neutral detergents as well as detergent formulationscontaining mixtures of alkaline detergent(s) plus substantially neutraldetergent(s).

The additives may be employed with alkaline detergents such asphosphates, complex phosphates, silicates, soda ash, caustic, boratesand the like which may contain alkali metal, amine and ammoniumsubstituents.

The term substantially neutral detergents includes anionic detergentssuch as exemplified by Oronite D-60 (about 60% sodium dodecyl benzenesulfonate and about 40% sodium sulfate) as well as nonionic detergentssuch as exemplified by Triton X-lOO (isooctylphenyl ether ofdecaethylene glycol). Anionic detergents such as alkali metal, amine andammonium salts of alkyl aryl sulfonic acids and nonionic detergents suchas alkyl aryl ether alcohols are illustrative of the varioussubstantially neutral detergents that may be employed in combinationwith one or more of the additives.

One of the conventional methods of studying skin irritation (e,g., inregard to humans) is to intradermally inject 0.5 cc. of the detergentformulation being tested into freshly shaved American chinchillarabbits. Observations are made after 24 hours and readings are made onthe basis of a scale of (for no irritation) to (for very badirritation). j

Tests were first started using male chincilla rabbits for test animalsin accordance with the above-mentioned conventional test procedure. Itwas found, however, that about /3 to about /2 of the test rabbits hadlarge, dark pigmented areas of skin that made the interpretation ofresults ditficult. Male albino rabbits were then obtained, and a seriesof conventional tests were made with both types of rabbits to determineif the same results, or at least the same relative results would beobtained with either kind of rabbit. The results ofv these comparisontests are shown in Table I. .A series of raw.

materials common to detergent formulations were injected atconcentrations of /2 ounce per gallon with an injection patternreading'from the back of the rabbit to the front:

where 1-2 were saline solution controls, 3-4, 5-6 and 7-8 were duplicateinjections of three raw materials (e.g., 3-4 were tetrasodiumpyrophosphate, 5-6 were Sterile solutions were used for all tests, andobservations were made after 24 hours;.

trisodium phosphate, etc.).

a rating was given as an average of the two duplicate spots based on thescale of 0 (no irritation) to 5 (ex-- tremely bad and spreadingirritation).

The data shown in Table I indicates that the degree of arritation wasgenerally only slightly higher with the albino rabbits than withchinchilla rabbits. Thus, male albino rabbits were used in allsubsequent tests.

TABLE I Comparison of results obtained with male American chinchillarabbits and male albino rabbits In subsequent tests, our procedureconsisted of injecting 0.5 ml. of solution intradermally into the sideof a freshly clipped male albino rabbit. It was found that by carefullyclipping the rabbits it was not necessary to shave the small amount ofremaining hair. By wetting the area with alcohol, injections andobservations were easily made. Tests were usually made at concentrationsof A, /2 and 1 ounce per gallon; these concentrations gave a degree ofirritation that was definite, but not excessive. Eight injections weremade to one rabbit side, and a replicate test was made in most cases onanother rabbit. Observations were made after 24 hours and ratings weregiven on the basis of a scale wherein 0 represents no irritation and 5represents very bad or maximum irritation. The effect of an additive on.the detergents was best detected when the detergent alone (without theadditive) had a rating of 2 to 3.

Th tests tabulated in Tables II -V were made on albino rabbits.Additives of various concentrations were employed. The concentration ofthe detergent formulations were A ounce per gallon, /2 ounce per gallonand 1 ounce per gallon. Replicates were run in most tests. The injectionpattern was from back to front:

where' 1-2 were 'saline controls, 3-5-7 were injections wherein oneconcentration ofpthe detergent was used,

in irri- The cetyl alcohol-urea complex in US. Patent 2,675,356.Lecithin was used TABLE III in on reducing sk rials were used as a basisfor comparing their etfectiveness with our additives.

described tation caused by various detergent components since it hasbeen alleged that the presence of 0.005 to the cell membranes againstthe irritating action of the detergent.

Summary of the effect of lecith 4-6-8 were tests wherein theconcentration of the detergent was the same as 3-5-7 and theconcentrations of the additive Were successively increased. Thus, in-

jections 3-5-7 were identical control injections of detergent for thethree difierent concentrations of additive 0.1% of soybean lecithin indetergent solutions protects employed, in injections 4-6-8. Theconcentration of the additives in the tables is based upon the totalsolids in the detergent plus additive compositions.

Table II shows the results of testing Sarkosyl NL-lOO (sodium N-lauroylsarcosinate), in conjunction with solul0 tions of detergents such assodium metasilicate, soda ash, trisodium phosphate, Triton X-100 andOronite D-60.

The results of these tests are given as to degree of irritation and datais presented in the form or" Treated Result and Untreated Result (e 03-4 shows that the aver- 544 1 033 35220u-055222-D55 n t n 1Q ,m m 4 aat 0 0 0 0 mm m 000 111000 00 fi M x no 0% a ma e e m a... a 0 U l m mtn n D. e 1 n n d m U n0 0 1H t .Ifi C S m 4442535551255110001115555555444555311523390115000 A1 s i 1 WA m 4 L22 L L a M w H M 2 000 000000 mst 8 F m a w m r a H w o .1 a v n... T 4 T l 2 h m mm 0000 000 V d m mn 00 00 0 0 0 000 .1 e 0 .1 o E o a n m L G C I u u g B C g n e n n m n n 1t A .I o s S w 0 u u .1 T f a a n n t a C u n C e S C .H e 0 t m m e r mm 0- n e 0 ew D u u m N M n m N n n 0 n 6 1. P w m 0 m m d c m m d w a ow n m o m o g m o o n n f t W 0 La ei m n m m 0 n mws a u m m mn m n m mmm o mwnrmwn n n niwhwwloi r C to m S an 4. u P namafififififififiefifim 5351 .BLP MM491 S C L2&1214 L24L24124124249249249 50 0 0 5 0 5 0 5 m 6 7 2 3 3 4 4 5 5 3 t g s d44455-3557011155555-065554333111KU5-HW222RWKNKN3332221 w .m m n m m maaa AZ 22 2 111 m5 5 i n 0 t C 8 OJ 3 83 S H n 9 c n e M M ME n m .v W 6c e P m n C 1 h n r 1 I U L1 1 Ir. 5 m n m n m m m 0 e fib m325551520500555555515030550552225551555555115 1 t d .1 d 0 C A d 8 a t.1 e e e 0 11 3 0 aazrrro 0 11 00 110 002121 0 t u a an 0 z m.. w l a w0 a m m M m M m m w t. s t 8 D4 T we t. /10 H W 2 N 1 n 6 N i ms .1 a mhe s m m m 00 00 00 m 0 000 00 000 0 0 0000 0000 m t. S l u 6 t O y u t 0t ..h M b m w H m 0 M 0m mow wt 3 E S E k n U N 0 mm 1 v e L m w u. e nn u a n r .1 t nnm B S n m n u n n u n w W 0 A c n i r a ll. y .1 ad H 0S O T 0 0 w H m1. no o .1 h 0 M n n o n s 0 t i 0 c cd e n n n h n m% ma e e m m r P ..L 0 e S e a L n u m a n 89 m D n e m m N m n m u u u nhe HM e so P A0 m 0 Wm f hm J m n m .m w m M C -m 0 n r n ma 6 e 0 g m ST e r V r e/ 1. m ND 3 duo r. y mt g p e Z r 1 n t mnmmwlw mh m wmmm 0mm d 0 0 l c a m S s nikb e1 o( C H n m r "n S a S 6 46 We. M 0 o k n mA JMWJ wJMWJ05JAAMJ .A 0 a a t fifi S S 247mmZ491-0249249249100222492492492491002492491 Table V shows the effect ofsodium N-lauroyl sarcote upon a composition that contains more than oneand cetyl alcohol-urea complex, respectively; these matedetergentproduct.

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5 TABLE v Eflect of additives on reducing skin irritation caused bydetergent formulation XF-200 1 Reaction at 1 Oz./Gal of FormulatedProduct Cone. of Additive, Additive Percent of Replicate 1 Replicate 2Total Solids With- With With- Without out Sarkosyl N L-100 2. 44 2 1. 52 1 Cetlyl Alcohol-Urea Com- 9. 1 1. 6 2 2 ex. p Do 4. 76 1. 0.5 2 1 D02. 44 l. 5 0 2 1 l Formulation XF-200: Percent by Weight Sodiumtripolyphosphafn 22.00 Sodium metasilicate 16.00 Sodiumcarboxymethylcellulose 0.23 Soda A sh 58. 27 Sodium dodecyl benzenesulfonate 2. 80 Ethylene glycoL 0. 70

The additives have been shown to be efiective when employed with thedetergent in quantities as low as about 0.1% by weight (based upon theweight of the total solids in the detergent plus additive compositions)as shown in Table II, but we do not limit the invention to thisconcentration, although in order to insure the most effective results,we prefer not to use less than this amount. However, it is desirable notto employ more than about 5% additive by weight. The term N-higher acylderivatives" shall hereinafter refer to water-soluble N- higher acylsarcosin salts (i.e., amine salts, alkali metal salts, ammonium salts)and/or materials that form N- higher acyl sarcosins and/ orwater-soluble salts of said N-higher acyl sarcosins upon hydration orwhen in contact with the skin.

Although the present invention has been described in conjunction withpreferred embodiments, it is to be understood that modifications andvariations may be resorted 6 to Without departing from the spirit andscope of the invention, as those skilled in the art will readilyunderstand. Such variations and modifications are considered to bewithin the purview and scope of the invention and appended claims.

We claim:

1. A substantially non-skin irritating nonacid detergent compositionhaving an additive which reduces the skin irritation that is normallyinduced by nonacid detergent compositions, said composition consistingessentially of: a synthetic organic detergent from the group consistingof sodium higher alkylbenzene sulfonates and higher alkylphenyl ethersof polyethylene glycol, and at least 0.1% by weight, based on the totalsolids, of a watersoluble additive which reduces the skin irritationnormally induced by said organic detergents, said additive being amember from the group consisting of N-lauroyl sarcosin and water-solublealkali salts thereof, said synthetic organic detergent being present insaid composition in an amount in excess of said additive.

2. The composition of claim 1 which includes an alkaline inorganicdetergent which serves as a detergent builder.

References Cited in the file of this patent UNITED STATES PATENTS2,528,378 Mannheimer Oct. 31, 1950 2,619,467 Isbell Nov. 25, 19522,675,356 Woodworth et al Apr. 13, 1954 FOREIGN PATENTS 360,982 GreatBritain Nov. 16, 1931 459,039 Great Britain Dec. 28, 1936 OTHERREFERENCES Surface Active Agents, by Schwartz et al., pub. byInterscience Pub. Inc., N.Y. (1949), p. 35.

Surface Activity, by Moilliet et al., pub. by E. & F. N. Spon, Ltd.,London (1951), p. 318.

UNITED STATES PATENT OFFICE EiiCAIE OF CORRECTION Patent No., 2,962 448November 29, 1960 Vladimir Dvorkovitz et alo It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent, should read as corrected below,

Column 1. line 22. for "sarcosimate" read sarcosinate line 62 for"chincilla read chinchilla column 2, line 19 for "arritation" readirritation line 61, for "Th" read The column 3, line 7, for "tables"read Tables column 5 TABLE V in the heading to the last column thereoffor With read With Signed and sealed this 10th day of October 1961(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer I Commissioner ofPatents USCOMM-DC

1. A SUBSTANTIALLY NON-SKIN IRRITATING NONACID DETERGENT COMPOSITIONHAVING AN ADDITIVE WHICH REDUCES THE SKIN IRRITATION THAT IS NORMALLYINDUCED BY NONACID DETERGENT COMPOSITIONS, SAID COMPOSITION CONSISTINGESSENTIALLY OF: A SYNTHETIC ORGANIC DETERGENT FROM THE GROUP CONSISTINGOF SODIUM HIGHER ALKYLBENZENE SULFONATES AND HIGHER ALKYLPHENYL EHTERSOF POLYETHYLENE GLYCOL, AND AT LEAST 0.1% BY WEIGHT, BASED ON THE TOTALSOLIDS, OF A WATERSOLUBLE ADDITIVE WHICH REDUCES THE SKIN IRRITATIONNORMALLY INDUCED BY SAID ORGANIC DETERGENTS, SAID ADDITIVE BEING AMEMBER FORM THE GROUP CONSISTING OF N-LAUROYL SARCOSIN AND WATER-SOLUBLEALKALI SALTS THEREOF, SAID SYNTHETIC ORGANIC DETERGENT BEING PRESENT INSAID COMPOSITION IN AN AMOUNT IN EXCESS OF SAID ADDITIVE.